Compatibilization and morphology development of immiscible ternary polymer blends

We report a novel and effective strategy that compatibilizes three immiscible polymers, polyolefins, styrene polymers, and engineering plastics, achieved by using a polyolefin-based multi-phase compatibilizer. Compatibilizing effect and morphology development are investigated in a model ternary immiscible polymer blends consisting of polypropylene (PP)/polystyrene(PS)/polyamide(PA6) and a multi-phase compatibilizer (PP-g-(MAH-co-St) as prepared by maleic anhydride (MAH) and styrene (St) dual monomers melt grafting PP. Scanning electron microscopy (SEM) results indicate that, as a multi-phase compatibilizer, PP-g-(MAH-co-St) shows effective compatibilization in the PP/PS/PA6 blends. The particle size of both PS and PA6 is greatly decreased due to the addition of multi-phase compatibilizer, while the interfacial adhesion in immiscible pairs is increased. This good compatibilizing effect is promising for developing a new, technologically attractive method for achieving compatibilization of immiscible multi-component polymer blends as well as for recycling and reusing of such blends. For phase morphology development, the morphology of PP/PS/PA6 (70/15/15) uncompatibilized blend reveals that the blend is constituted from PP matrix in which are dispersed composite droplets of PA6 core encapsulated by PS phase. Whereas, the compatibilized blend shows the three components strongly interact with each other, i.e. multi-phase compatibilizer has good compatibilization between the various immiscible pairs. For the 40/30/30 blend, the morphology changed from a three-phase co-continuous morphology (uncompatibilized) to the dispersed droplets of PA6 and PS in the PP matrix (compatibilized).     

Influences of component ratio of minor phases and charge sequence on the morphology and mechanical properties of PP/PS/PA6 ternary blends

In this study, influences of both component ratio of minor phases and charge sequence on the morphology and mechanical performance in typical ternary blends, polypropylene (PP)/polystyrene (PS)/polyamide-6 (PA6), have been studied. Reactive compatibilization of the blends has been carried out using multi-monomer melt grafted PP with anhydride groups and styrene segments. For uncompatibilized blends, scanning electron microscope (SEM) and selective solvent extraction showed that the blends presented a core–shell morphology with PS as shell and PA6 as core in the PP matrix, in spite of the component ratio and charge sequence. The shell thickened and droplet size decreased with increasing the PS/PA6 component ratio. While for compatibilized blends, the addition of compatibilizers resulted in a significant reduction of the dispersed droplet size and the phase structure of the dispersed phases was greatly dependent on the charge sequence. When the blending of PA6, g-PP, and PP are preceded, the encapsulation structure reversed into the structure of PS phase encapsulated by PA6 phase, which led to better tensile and flexural strength of the blends.     

Relaxation behavior of polymer blends with complex morphologies: Palierne emulsion model for uncompatibilized and compatibilized PP/PA6 blends

This paper deals with the dynamic rheological behavior of polypropylene/polyamide6 (PP/PA6) uncompatibilized blends and those compatibilized with a maleic anhydride grafted PP (PP/PP-g-MAH/PA6). The terminal relaxation times of the blends predicted by the Palierne emulsion model were compared with those obtained from experimental relaxation time spectra. The Palierne model succeeded well in describing PP/PA6 uncompatibilized blends with relatively low dispersed phase contents (10 wt%) and failed doing so for those of which the dispersed contents were high (30 wt%). It also failed for the compatibilized ones, irrespective of the dispersed phase content (10 or 30 wt%) and whether or not interface relaxation was taken into consideration. In the case of the uncompatibilized blend with high dispersed-phase content, interconnections among inclusions of the dispersed phase were responsible for the failure of the Palierne model. As for the compatiblized blends, in addition to particle interconnections, the existence of emulsion-in-emulsion (EE) structures was another factor responsible for the failure of Palierne model. A methodology was developed to use Palierne emulsion model upon taking into account the effects of the EE structure on the viscosity of the continuous phase and the effective volume fraction of the dispersed phase.     

Confined crystallization phenomena in immiscible polymer blends with dispersed micro- and nanometer sized PA6 droplets, part 2: reactively compatibilized PS/PA6 and (PPE/PS)/PA6 blends

In this paper the relation between the blend phase morphology and the fractionated crystallization behavior of PA6 in reactively compatibilized immiscible PS/PA6 and (PPE/PS)/PA6 immiscible blends is studied. Reactive compatibilization is used as an effective tool for controlling the blend phase morphology, and to reduce the PA6 dispersed droplet size. As reactive compatibilizers, SMA2 and SMA17 are used, which differ in their level of miscibility with the amorphous PS and (PPE/PS) components. With SMA2 a strong shift of PA6 crystallization to much higher supercoolings than before is found after compatibilization resulting in crystallization at temperatures as low as 85 °C. This is ascribed to the strong decrease of the droplet sizes down to 100-150 nm. Nucleation experiments show that heterogeneous bulk nucleation can be reintroduced in the submicron-sized PA6 droplets by adding enough nucleating agents of sufficient small size. The degree of fractionated crystallization is found to depend on the interface between PA6 droplets and surrounding medium, as it is influenced by vitrification of the matrix polymer and by the location of the compatibilizers SMA2 and SMA17. The method used for mixing the reactive compatibilizer with the blend components also affects the fractionated crystallization process.     

Compatible blends of polypropylene with an amorphous polyamide

Compatible polymer blends of polypropylene (PP) with an amorphous polyamide (aPA) were obtained through reactive compatibilization by adding 20% maleic anhydride‐modified copolymer (PP‐g‐MA) to the blends. The blends were made up of a pure PP phase and an aPA‐rich phase where very small amounts of PP were detected. The dispersed phase particle size decreased considerably indicating that compatibilization occurred. Young's modulus of the compatibilized blends increased with respect to that of the uncompatibilized ones. The compatibilized blends were highly ductile, and the impact strength also improved, proving that compatibilization occurred under a broad range of experimental conditions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Reactively formed block and graft copolymers as compatibilizers for polyamide 66/PS blends

Phthalic anhydride terminated polystyrene (PS-An) and styrene-maleic anhydride copolymer (SMA) were compared as a compatibilizer at low loadings (<10 wt%) in 70/30 polyamide 66 (PA66)/polystyrene (PS) blends. Compatibilization efficiency was judged by morphology of the blends and the extent of interfacial coupling to copolymer. Fluorescent labels of functional PS's (anthracene and pyrene for PS-An and SMA, respectively) allowed the detection of small amounts of reactively formed block (PA66-b-PS) or graft copolymer (SMA-g-PA66) in the blends via gel permeation chromatography with a fluorescence detector. Extremely fast reactions giving >60% conversion in 0.5 min mixing were observed regardless of the molecular weight, the structure, and the amount of the functional PS's. Interfacial stability of the reactively formed copolymers was estimated by micelle formation in the bulk phases and the interfacial coverage, Σ. PS-An with higher molecular weight (37 kg/mol) was most effective as a compatibilizer at the interface, showing less tendency to form microemulsions by suppressing interfacial roughening. However, a large portion of PA66-b-PS from low molecular weight PS-An (10 kg/mol) and SMA-g-PA66 from random functional SMA (16 kg/mol) migrated to the bulk phase to form micelles even at <2 wt% loadings. Blends of PA66 with syndiotactic PS compatibilized with PS-An gave very similar morphology to the PA66/PS blends indicating that these conclusions apply also to PA66/sPS blends.     

Melt rheological properties of polypropylene–polyamide6 blends compatibilized with maleic anhydride‐grafted polypropylene

The melt rheological properties of binary uncompatibilized polypropylene–polyamide6 (PP–PA6) blends and ternary blends compatibilized with maleic anhydride‐grafted PP (PP–PP‐g‐MAH–PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value δ between these two series of data was obtained. In binary PP–PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and δ was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of δ increased with the dispersed phase composition. In ternary PP–PP‐g‐MAH–PA6 systems, when the compatibility between PP and PA6 was enhanced by PP‐g‐MAH, the elongation and break‐up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the δ values of the ternary blends and the larger the positive deviation. Unlike uncompatibilized blends, under high shear stress with higher dispersed phase content, the PP‐g‐PA6 copolymer in compatibilized blends was pulled out from the interface and formed independent micelles in the matrix, which resulted in reduced total apparent shear viscosity. The δ value decreased with increasing shear stress. Copyright © 2006 Society of Chemical Industry     

Effect of reactive compatibilisation on the phase morphology and tensile properties of PA12/PP blends

Both uncompatibilized and compatibilized blends based on polyamide 12 (PA12) and isotactic polypropylene (PP) were prepared in a Brabender Plastograph®. The compatibiliser used was maleic anhydride functionalized polypropylene (PP‐g‐MA). Phase morphology of the blends was inspected in scanning electron microscope (SEM) on cryogenically fractured etched surfaces of the specimens. PA12/PP blends possessed a nonuniform and unstable morphology owing to the incompatibility between their constituents. Addition of compatibiliser improved the interfacial characteristics of the blends by retarding the rate of coalescence. So, the phase morphology became more fine, uniform, and stable. Tensile properties of both uncompatibilized and compatibilized blends were measured as a function of blend composition and compatibiliser concentration. Uncompatibilized blends displayed inferior mechanical properties to compatibilized ones; especially for those containing 40–60 wt % of PP. Reactive compatibilisation of blends was found to be efficient and improved the tensile strength of the blends considerably. Addition of PP‐g‐MA improved the interfacial adhesion, decreased the interfacial tension, and thereby, enhanced the tensile strength by 85%. Finally, various models were adopted to describe the tensile strength of the blends. The experimental data exhibited a reasonably good fit with Nielsen's first power law model. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Phase morphology and stability of co-continuous (PPE/PS)/PA6 and PS/PA6 blends: effect of rheology and reactive compatibilization

(PPE/PS)/PA6 and PS/PA6 blends were prepared by means of melt-extrusion. They were compatibilized using the reactive styrene-maleic anhydride copolymer with 2 wt% maleic anhydride (SMA2). The effect of compatibilization on the phase inversion and the stability of the resulting co-continuous blend structures were investigated using scanning electron microscopy, dissolution and extraction experiments. The onset of co-continuity shifted towards lower PA6 concentrations according to the change in blend viscosity ratio. The melting order of the components inside the extruder could result in a change in the observed co-continuity interval in slowly developing phase morphologies. The unmodified co-continuous blends were not stable and did break-up into a droplet/matrix type of morphology upon annealing in the melt depending on the blend composition. Although the stability of the threads during annealing improved upon compatibilization because of the lower resulting interfacial tension, the decreased possibility for recombination and coalescence during flow reduced the co-continuous region for the compatibilized blends. It is proposed that a dynamic equilibrium between break-up and recombination phenomena after the initial network formation is necessary to maintain the network structure.     

Phase morphology,thermomechanical, and crystallization behavior of uncompatibilized and PP‐g‐MAH compatibilized polypropylene/polystyrene blends

In this article, we discuss the phase morphology, thermal, mechanical, and crystallization properties of uncompatibilized and compatibilized polypropylene/polystyrene (PP/PS) blends. It is observed that the Young's modulus increases, but other mechanical properties such as tensile strength, flexural strength, elongation at break, and impact strength decrease by blending PS to PP. The tensile strength and Young's modulus of PP/PS blends were compared with various theoretical models. The thermal stability, melting, and crystallization temperatures and percentage crystallinity of semicrystalline PP in the blends were marginally decreased by the addition of amorphous PS. The presence of maleic anhydride‐grafted polypropylene (compatibilizer) increases the phase stability of 90/10 and 80/20 blends by preventing the coalescence. Hence, finer and more uniform droplets of PS dispersed phases are observed. The compatibilizer induced some improvement in impact strength for the blends with PP matrix phase, however fluctuations in modulus, strength and ductility were observed with respect to the uncompatibilized blend. The thermal stability was not much affected by the addition of the compatibilizer for the PP rich blends but shows some decrease in the thermal stability of the blends, where PS forms the matrix. On the other hand, the % crystallinity was increased by the addition of compatibilizer, irrespective of the blend concentration. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42100.     

Study of the properties of compatibilized ABS/PA6 blends using response surface methodology

Styrene‐(maleic anhydride) copolymer (SMA) compatibilized blends of acrylonitrile‐butadiene rubber (ABS) and polyamide 6 (PA6) with a variety of compositions and compatibilizer levels were prepared at various screw speeds in a corotating twin screw extruder. A Box–Behnken model for three variables, with three levels, was chosen as an experimental design, and the mechanical properties of the blends were considered as the responses. Each response was analyzed and formulated versus the considered factors by the use of response surface methodology. Impact resistance increased with increased SMA concentration and reduced screw speed. In compatibilized samples, with an increase in PA6 content, higher impact resistance was observed. Increasing PA6 content and SMA concentration, as well as decreasing screw speed, gave improvements in both tensile and flexural strengths. In each case, all of the correlations among factors were studied. Grafting of SMA was proved by detecting the graft copolymer (SMA‐PA6) formed through extraction in formic acid and FTIR spectroscopy. Compared with uncompatibilized blends, compatibilized samples displayed more uniform and finer particle sizes, thereby proving the compatibilizing effect of the graft copolymer. The asymmetry trend in dispersed particle size before and after the phase inversion became more differentiated in the presence of the compatibilizer. Adding SMA lowered the phase inversion composition (based on PA6), whereas higher screw speed increased it. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Cover Image,Volume 138, Issue 9

Blends of polypropylene (PP), polyamide 6 (PA6), and biodegradable polymers (BPs) such as poly(D,L-lactic acid) (PDLLA), poly(lactic acid-co-ε-caprolactone) (poly[LA-co-ε-CL]) and poly(ε-caprolactone) (PCL) were prepared using a twin-screw mini-extruder. The composition of the blend PP/PA6 was fixed at a mass proportion of 70/30, and the compatibilized blends contain 5 wt% of each BP. The morphology observed through scanning electronic microscopy, the dynamic mechanical thermal properties (DMTA), and the biodegradation test after composting and performing optical microscopy (OM) of the blends were investigated. The blend PP/PA6 compatibilized with polypropylene grafted with maleic anhydride (PPMA) was also obtained and used as a reference. The results showed that the PP/PA6/PPMA revealed a more homogeneous morphology and resulted in higher modulus; nevertheless, the sample obtained with the lower molar mass PDLLA as an alternative for PPMA showed a storage modulus behavior close to the reference material. Poly(LA-co-ε-CL) and PCL also showed changes in the morphology of the PA6 dispersed phase. Positive results were observed in the biodegradation test examined by OM for all samples containing BPs. The novelty of this work was to employ BPs as compatibilizing agents of the blends comprising PP/PA6, producing ternary blends with superior mechanical properties due to the better dispersion of the phases.     

Morphology development of in situ compatibilized semicrystalline polymer blends in a co-rotating twin-screw extruder

This paper concerns the morphology development of in situ compatibilized semicrystalline polymer blends in a co-rotating, intermeshing twin-screw extruder, using polypropylene (PP) and polyamide 6 (PA-6) blends as model systems. The morphology of in situ compatibilized blends develops much faster that of mechanical ones. The size of the dispersed phase (PA-6) undergoes a 10⁴ fold reduction from a few millimeters to sub-micron during its phase transition from solid pellets to a viscoelastic fluid. The final morphology is reached as soon as the phase transition is completed, which usually requires only a small fraction of the screw length in a co-rotating twin screw extruder. Screw profiles and processing conditions (screw speed, throughput and barrel temperature) control the PA-6's melting location and/or rate, but do not have significant impact on the ultimate morphology and mechanical properties of in situ compatibilized blends. The finding that morphology of PP/PA-6 reactive blend develops rapidly makes it possible to produce compatibilized PP/PA-6 blends by the so-called one-step reactive extrusion. It integrates the traditionally separated free radical grafting of maleic anhydride onto PP and the compatibilization of PP/PA-6 into a single extrusion step.     

Novel reactive compatibilization strategy on immiscible polypropylene and polystyrene blend

Polypropylene (PP) and polystyrene (PS) are immiscible and incompatible. Since both PP and PS components possess no reactive functional group, reactive compatibilization of a PP/PS blend is impossible unless certain reactive functional groups are imparted to either PP or PS. In this study we provide a simple approach to reactively compatibilize the nonreactive PP/PS blend system by physically functionalizing PP and PS with the addition of maleic anhydride grafted PP (PP‐g‐MA) and styrene maleic anhydride random copolymer (SMA), respectively. An epoxy monomer, serving as a coupler and possessing four epoxy groups able to react with the maleic anhydride of PP‐g‐MA and SMA, was then added during melt blending. Observations of the finer PS domain sizes and improved mechanical properties support the plausibility of reactive compatibilization of this nonreactive PP/PS blend by combining physically functionalized PP and PS with tetra‐glycidyl ether of diphenyl diamino methane (TGDDM) in a one‐step extrusion process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Toughening of polypropylene with styrene/ethylene‐butylene/styrene tri‐block copolymer: Effects of reactive and nonreactive compatibilization

The effects of compatibilization on the toughening of polypropylene (PP) by melt blending with styrene/ethylene‐butylene/styrene tri‐block copolymer (SEBS) in a twin‐screw extruder were investigated. The compatibilizers used were SEBS functionalized with maleic anhydride (SEBS‐g‐MA), PP functionalized with acrylic acid (PP‐g‐AA), and bifunctional compound p‐phenylenediamine (PPD). The effects of the compatibilization were evaluated through the mechanical properties as well as through the determination of the phase morphology of the blends by scanning electron microscopy. Reactive compatibilized blends show up to a 30‐fold increase in impact strength compared with neat PP; likely the result of the reaction of the bifunctional compound (PPD) with the acid acrylic and maleic anhydride groups, this increase in strength rendered both morphological and mechanical stability to these blends. The addition of PPD to the blends significantly changed their phase morphologies, leading to larger average diameters of the dispersed particles, probably as a result of the morphological stabilization at the initial processing steps during extrusion, with the occurrence of chemical reactions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3466–3479, 2002     

Toughening of polypropylene with styrene/ethylene‐butylene/styrene triblock copolymer: Effects of reactive and nonreactive compatibilization

The effects of the compatibilization on the toughening of polypropylene (PP) by melt blending with styrene/ethylene‐butylene/styrene triblock copolymer (SEBS) in a twin‐screw extruder were investigated. The compatibilizers used were an SEBS functionalized with maleic anhydride, a PP functionalized with acrylic acid, and a bifunctional compound, p‐phenylenediamine (PPD). The effects of the compatibilization were evaluated through the mechanical properties and by the determination of the phase morphology of the blends by scanning electron microscopy. Reactive compatibilized blends show up to a 30‐fold increase in impact strength compared to neat PP, which was likely to have been due to the reaction of the bifunctional compound (PPD) with the acid acrylic and maleic anhydride groups, which rendered both morphological and mechanical stability to these blends. The addition of the PPD to the blends significantly changed their phase morphologies, leading to larger dispersed particles' average diameters, probably due to the morphological stabilization at the initial processing steps during extrusion, with the occurrence of the chemical reactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1081–1094, 2003     

Compatibilization of polypropylene/nylon 6 blends with a polypropylene solid‐phase graft

The compatibilization of polypropylene (PP)/nylon 6 (PA6) blends with a new PP solid‐phase graft copolymer (gPP) was systematically studied. gPP improved the compatibility of PP/PA6 blends efficiently. Because of the reaction between the reactive groups of gPP and the NH₂ end groups of PA6, a PP‐g‐PA6 copolymer was formed as a compatibilizer in the vicinity of the interfaces during the melting extrusion of gPP and PA6. The tensile strength and impact strength of the compatibilized PP/PA6 blends obviously increased in comparison with those of the PP/PA6 mechanical blends, and the amount of gPP and the content of the third monomer during the preparation of gPP affected the mechanical properties of the compatibilized blends. Scanning electron microscopy and transmission electron microscopy indicated that the particle sizes of the dispersed phases of the compatibilized PP/PA6 blends became smaller and that the interfaces became more indistinct in comparison with the mechanical blends. The microcrystal size of PA6 and the crystallinity of the two components of the PP/PA6 blends decreased after compatibilization with gPP. The compatibilized PP/PA6 blends possessed higher pseudoplasticity, melt viscosity, and flow activation energy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 420–427, 2004     

Rheology and morphology of polytrimethylene terephthalate/ethylene propylene diene monomer blends in the presence and absence of a reactive compatibilizer

The dynamic rheological behavior and phase morphology of Polytrimethylene terephthalate (PTT) and ethylene propylene diene monomer (EPDM) uncompatibilized blends and those compatibilized with maleic anhydride grafted EPM (EPM‐g‐MA) were investigated. Effects of blend ratio and reactive compatibilization on the morphology and rheological properties of compatibilized and uncompatibilized blends have been analyzed. The viscosity ratio between the polymers was found to be sensitive to frequency which gave an indirect idea about the unstable morphology. The complex viscosity and dynamic modulus increased with increase in compatibilizer addition up to critical micelle concentration. Palierne and Choi‐Schowalter models were used to calculate the interfacial tension between the polymers. The interfacial tension decreased with the addition of compatibilizer up to CMC. It was also found that the minimum value of interfacial tension was found at CMC beyond that a levelling off is observed. The rheological properties of both compatibilized and uncompatibilized blends are found to be closely related to their phase morphology. POLYM. ENG. SCI., 50:1945–1955, 2010. © 2010 Society of Plastics Engineers     

The Effect of Multiple Compatibilizers on the Impact Properties of Polypropylene/Polystyrene (PP/PS) Blend

Effects of compatibilizers on impact properties of polypropylene/ polystyrene (PP/PS) blends were studied and carried out through melt blending using co- rotating twin-screw extruder. A combination of two compatibilizers, maleic anhydride grafted polypropylene (PP-g-MA) and styrene maleic anhydride (SMA) was applied into PP/PS blends. Results from the Izod impact strengths, SEM observations and contact angle measurements in PP(50)/PS(50) blends indicated a better compatibilization effect with the use of dual compatibilizers. This was most probably due to improved adhesion between phases in PP/PS blend systems. The use of dual compatibilizers in the blend compositions produced higher impact properties in the PP/PS blend systems compared to single compatibilizer system.     

Compatibilization efficiency of styrene–butadiene triblock copolymers in polystyrene–polypropylene blends with varying compositions

The compatibilization efficiency of two styrene‐butadiene‐styrene triblock copolymers with short (SB1) and long (SB2) styrene blocks was studied in polystyrene (PS)–polypropylene (PP) blends of composition 20, 50, and 80 wt % PS. The supramolecular structure of the blends was determined by small‐angle X‐ray scattering, and the morphology was studied with transmission electron microscopy and scanning electron microscopy. Structural changes in both the uncompatibilized and compatibilized blends were correlated with the values of tensile impact strength of these blends. Even though the compatibilization mechanisms were different in blends with SB1 and SB2, the addition of the block copolymers to the PS–PP 4/1 and PS–PP 1/4 blends led to similar structures and improved the mechanical properties in the same way. These block copolymers had a very slight effect on the impact strength in PS–PP 1/1 blends, exhibiting a nearly cocontinuous phase morphology. The strong migration of SB2 copolymers to the interface and of SB1 copolymers away from the interface were detected during the annealing of compatibilized PS–PP 4/1 blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2431–2441, 2004